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EP0692035B1 - Recuperation de cerium a partir de minerai contenant du fluorure - Google Patents

Recuperation de cerium a partir de minerai contenant du fluorure Download PDF

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Publication number
EP0692035B1
EP0692035B1 EP93909459A EP93909459A EP0692035B1 EP 0692035 B1 EP0692035 B1 EP 0692035B1 EP 93909459 A EP93909459 A EP 93909459A EP 93909459 A EP93909459 A EP 93909459A EP 0692035 B1 EP0692035 B1 EP 0692035B1
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EP
European Patent Office
Prior art keywords
cerium
fluoride
leachate
solution
boron
Prior art date
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EP93909459A
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German (de)
English (en)
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EP0692035A1 (fr
Inventor
Paula J. Bosserman
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Union Oil Company of California
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Union Oil Company of California
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Priority claimed from US07/584,729 external-priority patent/US5207995A/en
Application filed by Union Oil Company of California filed Critical Union Oil Company of California
Priority to AT93909459T priority Critical patent/ATE165626T1/de
Publication of EP0692035A1 publication Critical patent/EP0692035A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/247—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C01F17/265—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • This invention relates to recovery of cerium values from fluoride-containing rare earth ores such as bastnasite.
  • the principal rare earth source mineral in the United States is bastnasite, a mixture of lanthanide fluorocarbonates. Processing of bastnasite comprises crushing, flotation, roasting, and leaching steps that accomplish progressive separation and concentration of the various rare earth values contained in the ore see e.g. GB-A-1119720. It has proven especially difficult to recover purified cerium in high yield. Demand for cerium is presently increasing, and improvement in the yield of cerium from bastnasite processing is needed.
  • the present invention provides methods, as given by independent claims 1, 29, 36 and 47, for increasing the yield of cerium values from fluoride-containing mixtures such as ores and ore concentrates.
  • a process for solubilizing a cerium oxide which comprises: contacting the cerium oxide with a leach solution containing a strong acid and a species comprising boron and fluorine to form a leachate containing solubilized cerium.
  • a process for recovering cerium values from a mixture comprising a cerium oxide and a cerium fluoride which comprises: contacting the mixture with a leach solution containing hydrochloric acid and a boron compound capable of reacting with the fluoride to form a leachate containing solubilized cerium and a reaction product of the fluoride and the boron compound.
  • the solubilization of cerium values from a solid mixture may be improved by treating the mixture with a solution of hydrochloric acid and a boron compound such as boric acid.
  • This solution is preferably capable of dissolving substantially all the cerium values present, including the cerium fluorides which are insoluble in hydrochloric acid alone.
  • fluoride may be dissolved and converted to tetrafluoroborate ion, BF 4 - , which catalyzes the solubilization of ceric oxide.
  • the insoluble residue, now depleted of cerium values, may be removed and the cerium-enriched solution further treated as described below for removal of the tetrafluoroborate.
  • tetrafluoroborate ion is preferably removed from the cerium-enriched solution.
  • a source of soluble potassium ion is added to the cerium-enriched solution to precipitate insoluble potassium tetrafluoroborate, which is removed. Removal of tetrafluoroborate at this point avoids the loss of cerium values as insoluble cerium tetrafluoroborate when the cerium-enriched solution is subjected to further processing for removal of non-cerium constituents.
  • the resulting cerium-enriched, fluoride-depleted solution can then be subjected to cerium recovery steps similar to those employed with conventional cerium-containing solutions to provide improved yields of cerium.
  • Bastnasite ore typically comprises from about 5 to 8 and typically about 6 weight percent rare earths calculated as rare earth oxides LnO (rare earth value of 6%).
  • the balance comprises what are considered impurities such as the associated quartz, barite, calcite and strontianite.
  • the ore is pulverized and ground to a size that will pass through a 100 mesh screen.
  • the particle size is within the range of from about 1 to 100 microns and preferably within the range of from about 5-25 microns.
  • the ground ore is subjected to a flotation process to separate a substantial amount of impurities from the rare earth compounds.
  • a flotation process to separate a substantial amount of impurities from the rare earth compounds.
  • the bastnasite is separated from associated minerals such as quartz, barite, calcite and strontianite. This process produces a concentrate comprising about 60 weight percent rare earths calculated as oxides.
  • the concentrate is then subjected to a first acid leach with a dilute hydrochloric acid (pH about 1.0) to remove some of the alkaline earth constituents of the concentrate.
  • a dilute hydrochloric acid pH about 1.0
  • This produces an enriched concentrate comprising approximately 70 weight percent rare earths calculated as oxides.
  • the enriched concentrate is then roasted, typically at about 400° C to about 800° C, in the presence of air.
  • the roasting step converts the fluorocarbonate mineral to a mixture of fluorides and oxides and oxidizes the cerium content to its tetravalent state.
  • the roasting step also oxidizes some of the remaining alkaline earth constituents to their corresponding oxides.
  • a typical roasted ore can comprise the oxides, carbonates, and/or fluorides of strontium, calcium, barium and magnesium, for example in concentrations, calculated as the oxides, of at least about 0.5, 7.0, 5.0 and 1.0 weight percent respectively.
  • the roasted ore is then subjected to a second acid leach, this time with a more concentrated acid solution.
  • the second leach utilizes approximately a 0.1 to 0.5N and preferably about a 0.2N hydrochloric acid.
  • the purpose of this leach is to remove the remaining alkaline earth constituents and to separate the cerium from the other rare earth oxides. A substantial proportion of the cerium is recovered as an insoluble residue ("cerium concentrate") while the solubilized rare earths are removed and sent to a separate solvent extraction facility for recovery.
  • the solid cerium concentrate from the second acid leach typically contains a mixture of cerium compounds including ceric oxide and cerium fluorides (e.g., cerous fluoride, ceric fluoride, and hydrous ceric fluoride), along with other constituents such as compounds of iron, thorium, alkaline earths, lead, and calcium.
  • ceric oxide and cerium fluorides e.g., cerous fluoride, ceric fluoride, and hydrous ceric fluoride
  • the solid cerium concentrate is next treated with a third acid leach, a still more concentrated hydrochloric acid solution (e.g., about 50 weight percent HCl), to solubilize the cerium values for further processing.
  • a third acid leach e.g., about 50 weight percent HCl
  • Cerium values that are not solubilized at this point are usually lost.
  • the ceric oxide dissolves, but the cerium fluorides are insoluble in the hydrochloric acid solution.
  • cerium values present as fluorides have usually been lost.
  • solubilization of cerium values from a solid, fluoride-containing mixture is improved by treating the mixture with a concentrated solution of a strong acid, i.e. , an acid that is highly ionized in aqueous solution, to which a suitable boron compound, such as boric acid, has been added.
  • a suitable boron compound is one which is capable of reacting with the fluoride in the mixture, including that present as cerium fluorides, to form a soluble complex of boron and fluorine, which complex in turn can be removed from the solution as tetrafluoroborate, e.g., by precipitation as a tetrafluoroborate salt.
  • Strong acids that can be used in the practice of this invention include, for example, hydrochloric acid, nitric acid, sulfuric acid, and mixtures thereof; hydrochloric acid is highly preferred.
  • the use of a boron compound in accordance with this invention has two significant advantages. First, the cerium fluorides are dissolved, so that the yield of cerium from the solid mixture is increased. Second, the tetrafluoroborate ion catalyzes the dissolution of ceric oxide, so that the cerium values are brought into solution faster and more efficiently. This decreases the time required for carrying out the acid leach step and increases the productivity of the process.
  • ceric oxide is essentially insoluble in pure, concentrated hydrochloric acid, but that a small concentration of soluble fluoride ion in the hydrochloric acid very effectively catalyzes the dissolution of the ceric oxide. It has now been found in the practice of this invention that a reaction product of a boron compound, such as boric acid, and a fluoride, such as a fluoride component of a cerium ore concentrate, is an even more effective catalyst than fluoride alone for the dissolution of ceric oxide in hydrochloric acid solution.
  • a boron compound such as boric acid
  • a fluoride such as a fluoride component of a cerium ore concentrate
  • the catalytic species is believed to be a complex of boron and fluorine, specifically a fluoroborate, more specifically the tetrafluoroborate ion, BF 4 - . It is also believed that the tetrafluoroborate ion is in equilibrium in the acid solution with another fluoroborate species, BF 3 OH - , which can be formed by hydrolysis of tetrafluoroborate ion, and such species may also have catalytic activity in the dissolution of ceric oxide. Other species comprising boron and fluorine may also exist in solution, such as large complexes comprising tetrafluoroborate or species existing in equilibrium with tetrafluoroborate.
  • fluoroborate means tetrafluoroborate and any species in solution comprising boron and fluorine which comprises or is in equilibrium with tetrafluoroborate.
  • the catalytic species can be present in proportions as small as about 0.01 mole per mole of cerium oxide, preferably at least about 0.05 mole per mole, more preferably at least about 0.1 mole per mole. Higher proportions can also be used.
  • cerium fluorides such as cerium fluorides present in admixture with cerium oxides in a cerium ore concentrate
  • sufficient boron compound is used to provide at least about 0.1 mole of boron per 4 moles of fluoride present in the cerium concentrate, and preferably at least about 0.5 mole of boron per 4 moles of fluorine. More preferably, sufficient boron compound is included to provide at least about 1 mole of boron for every 4 moles of fluorine present. In the embodiment most preferred at present, at least about 2 moles of boron are provided for every 4 moles of fluorine.
  • a substantial portion, e.g., at least about 10 weight percent, preferably at least about 25 percent, and more preferably at least about 50 percent, of all the cerium fluorides in the solid mixture is solubilized. The fluoride content thereof is converted to soluble species such as BF 4 - and, it is believed, BF 3 OH - ; and the cerium content is solubilized at the same time.
  • boron compound that reacts with fluoride in acid to form tetrafluoroborate ion can be used in the practice of this invention.
  • suitable boron compounds include boric acid and borates soluble in the leach solution, preferably alkali metal borates such as potassium borate and sodium borate (borax).
  • alkali metal borates such as potassium borate and sodium borate (borax).
  • borates added to the leach solution react to form boric acid in the solution.
  • additional mineral acid is needed to react with the borate.
  • boric acid itself is presently the most preferred boron compound for use in the process of the invention.
  • a solid mixture comprising cerium oxide and a fluoride is treated with a concentrated aqueous solution of hydrochloric acid in the presence of a boron compound such as boric acid.
  • the fluoride is typically a fluoride salt of a metal, usually a lanthanide metal, or a mixture of such fluorides.
  • the fluoride comprises one or more cerium fluorides.
  • the process of this invention is particularly beneficial in solubilizing mixtures of both ceric oxide and one or more cerium fluorides.
  • the ratio of cerium atoms present as oxide to cerium atoms present as fluoride is no less than about 1 to 9 and no greater than about 9 to 1.
  • the ratio is between about 1 to 5 and about 5 to 1, and more preferably between about 1 to 2 and about 2 to 1.
  • the ratio can be about 1 to 1; i.e., about half the cerium can be present in the form of oxide and about half in the form of fluorides.
  • the solid mixture typically is finely-divided, preferably having particle sizes no larger than about 10 microns. Larger particles take longer to dissolve.
  • the finely divided solid is slurried in water with the boric acid.
  • Sufficient concentrated hydrochloric acid to provide the desired concentration of HCl in the leach acid solution is then added slowly with mixing over a period of, for example, 2 to 3 hours.
  • the leach acid solution typically comprises at least about 50 weight percent HCl, preferably at least about 60 percent, and more preferably at least about 70 percent; and typically no more than about 90 percent, preferably no more than about 85 percent, and more preferably no more than about 80 percent HCl.
  • Leaching can be carried out at any temperature from ambient, e.g., about 20° C, up to the boiling point of the liquid/solid mixture, e.g., about 100° C at ambient pressure. Higher temperatures can be used if the leaching is carried out at elevated pressure. However, moderate temperatures at ambient pressure are preferred, e.g., between about 40° and about 90° C, preferably between about 50° and about 80° C. Temperatures in the range of about 60° to about 70°C, e.g., about 65° C, are most preferred. Leaching is carried out typically for about 3 to about 12 hours, preferably from about 5 to about 9 hours, with stirring. At the conclusion of the leach step, sufficient hydrochloric acid should still be present in the leachate to prevent reprecipitation of cerium compounds; preferably, the leachate is at least about 4N in hydrochloric acid concentration.
  • cerium values have been solubilized, any insoluble residue is removed, and the cerium-containing solution is processed for further purification and concentration of the cerium values.
  • the next step in processing the cerium-containing solution resulting from such a concentrated hydrochloric acid leach has generally involved adding a base to raise the pH of the solution sufficiently to precipitate certain impurities such as iron.
  • a base to raise the pH of the solution sufficiently to precipitate certain impurities such as iron.
  • a solution containing dissolved cerium ions and tetrafluoroborate ions is treated so as to remove tetrafluoroborate from the solution while leaving cerium in solution. Then, the pH of the solution can be raised to precipitate impurities without coprecipitating cerium values as cerium tetrafluoroborate.
  • the solution is treated with a substance that reacts with tetrafluoroborate ion to form an insoluble compound, which precipitates and is separated from the solution before the pH thereof is raised.
  • Compounds suitable for use in removing tetrafluoroborate from cerium-containing solutions in accordance with this invention include, without limitation, acid-soluble potassium compounds, preferably potassium salts of strong inorganic acids, such as the halides, nitrate, sulfate, and the like.
  • Potassium chloride is preferred because it does not introduce a type of anion not already present in the solution.
  • Potassium tetrafluoroborate has low solubility in the solution and therefore precipitates, removing tetrafluoroborate ion from the solution.
  • Sufficient potassium is added to combine with and precipitate out of solution a substantial portion of the tetrafluoroborate ion present, e.g., at least about 25 percent, preferably at least about 40 percent, and more preferably at least about 60 percent of the tetrafluoroborate ion.
  • sufficient potassium compound is added to provide at least about 0.5 mole, more preferably at least about 1 mole, of potassium ion per mole of boron present in the solution.
  • the potassium compound can be added at any stage of the leach step: at the beginning, or gradually during the leach period, or at the end. Preferably, it is added at the beginning, so that as tetrafluoroborate ion is formed in the solution, it reacts with the potassium ion and precipitates when the solubility limit of potassium tetrafluoroborate is reached. In this way, the concentration of tetrafluoroborate ion in solution is maintained below the solubility limit of cerous tetrafluoroborate, so that precipitation of cerous tetrafluoroborate is avoided.
  • solubilized cerium in the leachate it is desirable to achieve as high a concentration of solubilized cerium in the leachate as possible to avoid the difficulty of recovering the metal values in solid form from dilute solution. Higher concentrations facilitate further processing and eventual recovery of a solid cerium compound.
  • concentration of cerium ion In a hydrochloric acid leachate containing a substantial concentration of tetrafluoroborate ion, such as that resulting from the leaching of a cerium concentrate derived from bastnasite, the concentration of cerium ion must be kept relatively low, no higher than about 60 grams per liter, as cerium, to avoid the loss of cerium through unwanted precipitation of cerium tetrafluoroborate.
  • the addition of potassium to the leach solution during the leaching step maintains the concentration of tetrafluoroborate ion in the solution sufficiently below the solubility limit of cerium tetrafluoroborate and that a higher concentration of solubilized cerium can be achieved in the leachate without loss of cerium as cerium tetrafluoroborate.
  • the cerium concentration in the leachate can be at least about 90 grams per liter, preferably at least about 120 g/l, and more preferably at least about 150 g/l, as cerium.
  • the potassium tetrafluoroborate is removed, e.g., by filtration, leaving a solution which is enriched in cerium and depleted in fluoride.
  • a solution which is enriched in cerium and depleted in fluoride.
  • the solution can be treated for recovery of solid cerium carbonate in a manner similar to that used for treatment of cerium containing solutions obtained by conventional hydrochloric acid leaching of bastnasite.
  • the pH of the solution is raised sufficiently to precipitate iron compounds, e.g., to about 2.6, with a base such as aqueous sodium hydroxide solution.
  • the solution is filtered, a soluble sulfide such as sodium hydrogen sulfide is added to precipitate lead as lead sulfide, and the solution is again filtered.
  • the solution is reacidified, e.g., to about pH 1.0, and a soluble carbonate, preferably an alkali metal carbonate such as sodium carbonate solution, is slowly added.
  • cerium carbonate precipitates and is removed, for example, by filtration on a continuous belt filter. Carbonate addition is halted before undesirable compounds begin to precipitate in appreciable amounts, e.g., before the pH of the solution exceeds about 4.9.
  • the cerium carbonate is recovered from the filter and dried. Cerium carbonate of high purity, e.g., at least about 90 percent pure, preferably at least about 95 percent pure, can be made in this way.
  • a material containing at least one cerium component of bastnasite and at least one fluoride component of bastnasite can be contacted with a leach solution comprising concentrated hydrochloric acid, a suitable boron compound, and, preferably, a source of potassium ion.
  • Suitable materials include roasted and unroasted (raw) bastnasite, and residues thereof from prior processing operations that contain cerium and fluoride components.
  • the cerium component can be, for example, a cerium oxide (from roasted bastnasite) or cerium carbonate (from raw bastnasite).
  • the fluoride component preferably comprises at least one cerium fluoride component.
  • a leachate which comprises solubilized cerium, a fluoroborate species, e.g., tetrafluoroborate, alkaline earth metals, and other lanthanides, as well as impurities such as iron and lead.
  • cerium carbonates and cerium fluorides are solubilized, providing enhanced solubilization of cerium values from the bastnasite material.
  • the leachate can then be processed for isolation and recovery of the cerium values. For example, iron can be precipitated by raising the pH of the leachate, and then lead can be removed by precipitation as lead sulfide. Carbonate is then added to the filtered solution to precipitate lanthanide carbonates, leaving alkaline earth metal carbonates in solution.
  • the lanthanide carbonates are then roasted in the presence of oxygen to form lanthanide oxides, which are then contacted with a dilute hydrochloric acid leach to dissolve the non-cerium oxides, leaving the desired ceric oxide.
  • the ceric oxide can be recovered by filtration.
  • the leach solution was found to contain about 91% of all the cerium present in the Cerium Concentrate feed.
  • the feed contains a small amount of monazite (cerium phosphate), which is insoluble in hydrochloric acid solutions, and so the maximum theoretical yield of cerium from such feed in a hydrochloric acid based leachate system is about 94 to 97%.
  • the 91% yield of solubilized cerium achieved by practice of this invention closely approaches the theoretical yield.

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Abstract

L'invention concerne la récupération de cérium à partir de minerai contenant du fluorure tel que la bastnäsite. Le minerai est broyé, grillé et lessivé avec de l'acide chlorhydrique dilué pour produire un concentré du minerai. Le concentré est traité avec une solution d'acide chlorhydrique et d'acide borique pour solubiliser le cérium à récupérer et convertir le fluorure en tétrafluoroborate. Le tétrafluoroborate est séparé de la solution, par exemple par précipitation, et la solution est ensuite traitée pour la récupération du cérium. La séparation du tétrafluoroborate évite les pertes de cérium sous la forme de tétrafluoroborate de cérium (qui est insoluble) durant les traitements ultérieurs.

Claims (47)

  1. Procédé qui consiste à mettre en contact un mélange solide comprenant un oxyde de cérium et un fluorure avec une solution de lixiviation comprenant un acide fort et un composé du bore capable de réagir avec ledit fluorure.
  2. Procédé selon la revendication 1, dans lequel ledit composé du bore est choisi parmi l'ensemble comprenant l'acide borique et ses sels.
  3. Procédé selon la revendication 1 ou 2, dans lequel le mélange comprend un fluorure de cérium.
  4. Procédé selon la revendication 1 ou 2, dans lequel le mélange comprend de l'oxyde cérique.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel la solution de lixiviation comprend au moins 50 % en poids de HCl.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le composé du bore est présent en une quantité suffisante pour donner au moins environ 0,5 mole de bore pour 4 moles de fluor.
  7. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le composé du bore est présent en une quantité suffisante pour donner au moins 1 mole de bore pour 4 moles de fluor.
  8. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le composé du bore est présent en une quantité suffisante pour donner au moins 2 moles de bore pour 4 moles de fluor.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel le composé du bore et le fluorure réagissent pour former une espèce de fluoroborate.
  10. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel le composé du bore et le fluorure réagissent pour forme un ion tétrafluoroborate.
  11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel ledit oxyde de cérium est mis en contact avec une solution de fixiviation contenant un acide fort et une espèce contenant du bore et du fluor pour former un produit de lixiviation contenant du cérium solubilisé.
  12. Procédé selon la revendication 11, dans lequel l'oxyde de cérium est traité à une température d'au moins environ 40°C.
  13. Procédé selon la revendication 11, dans lequel l'oxyde de cérium est traité à une température d'au moins environ 60°C.
  14. Procédé selon la revendication 11, dans lequel ladite espèce est présente selon une proportion de moins de 1 mole par mole d'oxyde de cérium.
  15. Procédé selon la revendication 11, dans lequel ladite espèce est présente selon une proportion de moins d'environ 0,5 mole par mole d'oxyde de cérium.
  16. Procédé selon la revendication 1, dans lequel ledit mélange comprend un oxyde de cérium et un fluorure de cérium, le procédé consistant ;
       à mettre en contact ledit mélange d'oxyde de cérium et de fluorure de cérium avec une solution de fixiviation contenant de l'acide chlorhydrique et un composé du bore capable de réagir avec ledit fluorure pour former un produit de lixiviation contenant du cérium solubilisé et un produit de la réaction dudit fluorure et dudit composé du bore.
  17. Procédé selon la revendication 16, qui consiste à extraire dudit produit de lixiviation un composé comprenant du bore et du fluor.
  18. Procédé selon l'une quelconque des revendications 1 à 17, dans lequel ladite solution de lixiviation contient des ions potassium.
  19. Procédé selon la revendication 17, qui consiste à ajouter une source d'ion potassium audit produit de fixiviation, en une quantité suffisante pour provoquer la précipitation du tétrafluoroborate de potassium à partir dudit produit de lixiviation, et à extraire le tétrafluoroborate de potassium.
  20. Procédé selon la revendication 16, dans lequel ledit mélange d'oxyde de cérium et de fluorure de cérium comprend au moins 30 % en poids de cérium, calculé en oxyde cérique, et au moins environ 5 % en poids de fluorure.
  21. Procédé selon la revendication 16, dans lequel ledit mélange d'oxyde de cérium et de fluorure de cérium comprend au moins 45 % en poids de cérium, calculé en oxyde cérique, et au moins environ 7,5 % en poids de fluorure.
  22. Procédé selon la revendication 16, dans lequel ledit mélange d'oxyde de cérium et de fluorure de cérium comprend au moins 60 % en poids de cérium, calculé en oxyde cérique, et au moins environ 10 % en poids de fluorure.
  23. Procédé selon la revendication 17, dans lequel ledit produit de lixiviation contient au moins environ 90 g de cérium solubilisé par litre.
  24. Procédé selon la revendication 17, dans lequel ledit produit de lixiviation contient au moins environ 120 g de cérium solubilisé par litre.
  25. Procédé selon la revendication 17, dans lequel ledit produit de lixiviation contient au moins environ 150 g de cérium solubilisé par litre.
  26. Procédé selon la revendication 16, dans lequel le produit de lixiviation comprend en tant que cérium solubilisé au moins environ 70 % de l'ensemble du cérium initialement présent dans le mélange solide.
  27. Procédé selon la revendication 16, dans lequel le produit de lixiviation comprend en tant que cérium solubilisé au moins environ 80 % de l'ensemble du cérium initialement présent dans le mélange solide.
  28. Procédé selon la revendication 16, dans lequel le produit de lixiviation comprend en tant que cérium solubilisé au moins environ 90 % de l'ensemble du cérium initialement présent dans le mélange solide.
  29. Procédé selon pour récupérer du cérium à partir de bastnäsite, qui comprend l'étape consistant:
       à mettre en contact un matériau solide comprenant un constituant cérium et un constituant fluorure avec une solution d'un acide fort et d'un composé du bore capable de réagir avec ledit constituant fluorure, la solution étant suffisante pour former un produit de lixiviation contenant du cérium solubilisé et un produit de la réaction dudit composé du bore et dudit constituant fluorure, où ledit matériau solide est obtenu à partir de bastnäsite.
  30. Procédé selon la revendication 29, dans lequel ladite solution comprend de l'acide chlorhydrique.
  31. Procédé selon la revendication 29, dans lequel ladite solution comprend de l'acide sulfurique.
  32. Procédé selon la revendication 29, dans lequel ladite solution comprend de l'acide nitrique.
  33. Procédé selon la revendication 29, dans lequel le matériau solide comprend un oxyde de cérium et un fluorure de cérium.
  34. Procédé selon la revendication 30, dans lequel on utilise une quantité du composé du bore suffisante pour donner au moins environ 1 mole de bore pour 4 moles de fluor.
  35. Procédé selon l'une quelconque des revendications 29 à 34, qui consiste en outre :
    à traiter ledit produit de lixiviation avec une source d'ions potassium pour provoquer la précipitation du tétrafluoroborate de potassium; et
    à séparer ledit précipité dudit produit de lixiviation.
  36. Procédé pour récupérer le cérium partir de bastnäsite, qui consiste :
    à griller de la bastnäsite finement divisée, en présence d'oxygène ;
    à mettre en contact la bastnäsite grillée avec une solution diluée d'acide chlorhydrique, en une quantité suffisante pour dissoudre les constituants alcalino-terreux, en laissant un résidu solide comprenant des constituants cérium et fluorure: et
    à lixivier ledit résidu solide avec une solution plus concentrée d'acide chlorhydrique contenant un composé du bore choisi parmi l'ensemble comprenant l'acide borique et ses sels, pour former un produit de lixiviation contenant du sérium solubilisé et une espèce de fluoroborate.
  37. Procédé selon la revendication 36, qui consiste en outre à ajouter une source d'ion potassium au produit de lixiviation pour provoquer la précipitation du tétrafluoroborate de potassium, et à extraire du produit de fixiviation le tétrafluoroborate de potassium.
  38. Procédé selon la revendication 36, dans lequel ladite solution concentrée d'acide chlorhydrique contient aussi une quantité d'ion potassium suffisante pour provoquer la précipitation du tetrafluoroborate de potassium à partir du produit de fixiviation au cours de l'étape de lixiviation.
  39. Procédé selon la revendication 38, dans lequel le produit de lixiviation comprend du cérium dissous, constituant au moins 70 % du cérium initialement présent dans le résidu solide.
  40. Procédé selon la revendication 38, dans lequel le produit de lixiviation comprend du cérium dissous, constituant au moins 80 % du cérium initialement présent dans le résidu solide.
  41. Procédé selon la revendication 38, dans lequel le produit de fixiviation comprend du cérium dissous, constituant au moins 90 % du cérium initialement présent dans le résidu solide.
  42. Procédé selon la revendication 36, dans lequel la lixiviation est mise en oeuvre à une température comprise entre environ 40 et environ 90°C.
  43. Procédé selon la revendication 36, dans lequel la lixiviation est mise en oeuvre à une température comprise entre environ 50 et environ 80°C.
  44. Procédé selon la revendication 36, dans lequel la lixiviation est mise en oeuvre à une température comprise entre environ 60 et environ 70°C.
  45. Procédé selon la revendication 36, dans lequel le composé du bore est présent en une quantité suffisante pour donner au moins environ 1 mole de bore pour 4 moles de fluor dans le résidu solide.
  46. Procédé selon la revendication 36, dans lequel le composé du bore est présent en une quantité suffisante pour donner au moins environ 2 moles de bore pour 4 moles de fluor dans le résidu solide.
  47. Procédé qui consiste :
    à mettre à disposition une solution comprenant du cérium solubilisé à partir d'un solide comprenant de l'oxyde de cérium, par mise en contact dudit solide avec une solution de lixiviation contenant un acide fort et des composés du bore et du fluor ;
    à ajouter à ladite solution une quantité d'une source d'ion potassium suffisante pour provoquer la précipitation du tétrafluoroborate de potassium ; et
    à séparer de ladite solution ledit tétrafluoroborate de potassium.
EP93909459A 1990-09-19 1993-03-29 Recuperation de cerium a partir de minerai contenant du fluorure Expired - Lifetime EP0692035B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT93909459T ATE165626T1 (de) 1993-03-29 1993-03-29 Gewinnung von cer aus fluorid-enthaltenden erzen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/584,729 US5207995A (en) 1990-09-19 1990-09-19 Recovery of cerium from fluoride-containing ores
US08/026,502 US5433931A (en) 1990-09-19 1993-03-04 Recovery of cerium
PCT/US1993/002873 WO1994023075A1 (fr) 1990-09-19 1993-03-29 Recuperation de cerium a partir de minerai contenant du fluorure
CN93105197A CN1042145C (zh) 1990-09-19 1993-03-30 从含氧化铈和氟化物的固体混合物中回收铈的方法

Publications (2)

Publication Number Publication Date
EP0692035A1 EP0692035A1 (fr) 1996-01-17
EP0692035B1 true EP0692035B1 (fr) 1998-04-29

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EP93909459A Expired - Lifetime EP0692035B1 (fr) 1990-09-19 1993-03-29 Recuperation de cerium a partir de minerai contenant du fluorure

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EP (1) EP0692035B1 (fr)
JP (1) JP3415844B2 (fr)
CN (1) CN1042145C (fr)
DE (1) DE69318315D1 (fr)
NO (1) NO307660B1 (fr)
RU (1) RU2114204C1 (fr)
WO (1) WO1994023075A1 (fr)

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CN102605198A (zh) * 2012-01-13 2012-07-25 东北大学 一种氟碳铈矿的分解方法
US8337789B2 (en) 2007-05-21 2012-12-25 Orsite Aluminae Inc. Processes for extracting aluminum from aluminous ores
US9023301B2 (en) 2012-01-10 2015-05-05 Orbite Aluminae Inc. Processes for treating red mud
US9181603B2 (en) 2012-03-29 2015-11-10 Orbite Technologies Inc. Processes for treating fly ashes
US9260767B2 (en) 2011-03-18 2016-02-16 Orbite Technologies Inc. Processes for recovering rare earth elements from aluminum-bearing materials
US9290828B2 (en) 2012-07-12 2016-03-22 Orbite Technologies Inc. Processes for preparing titanium oxide and various other products
US9353425B2 (en) 2012-09-26 2016-05-31 Orbite Technologies Inc. Processes for preparing alumina and magnesium chloride by HCl leaching of various materials
US9382600B2 (en) 2011-09-16 2016-07-05 Orbite Technologies Inc. Processes for preparing alumina and various other products
US9410227B2 (en) 2011-05-04 2016-08-09 Orbite Technologies Inc. Processes for recovering rare earth elements from various ores
US9534274B2 (en) 2012-11-14 2017-01-03 Orbite Technologies Inc. Methods for purifying aluminium ions

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CN1045010C (zh) * 1995-04-12 1999-09-08 北京有色金属研究总院 一种从含氟硫酸稀土溶液中萃取分离铈的方法
CN100436611C (zh) * 2007-04-24 2008-11-26 北京科技大学 一种利用控制ph值来提纯铈的方法
FR2956413B1 (fr) * 2010-02-15 2012-03-09 Commissariat Energie Atomique Procede de production d'hydrogene par voie thermochimique, base sur l'hydrochloration du cerium.
RU2429199C1 (ru) * 2010-03-15 2011-09-20 Учреждение Российской академии наук Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра РАН (ИХТРЭМС КНЦ РАН) Способ очистки фторсодержащего редкоземельного концентрата
CN101967555B (zh) * 2010-10-25 2012-06-06 东北大学 一种活化后再浸出分解氟碳铈矿的方法
CN104313318A (zh) * 2014-09-29 2015-01-28 乐山盛和稀土股份有限公司 品位45%-60%的稀土氟碳酸铈矿浸矿工艺
CN104946887A (zh) * 2015-07-22 2015-09-30 中国恩菲工程技术有限公司 氟碳铈精矿的处理方法
CN104962762A (zh) * 2015-07-22 2015-10-07 中国恩菲工程技术有限公司 氟碳铈精矿的处理方法
CN109266838B (zh) * 2017-07-18 2020-08-28 有研稀土新材料股份有限公司 氟碳铈矿及含氟碳铈矿的混合矿的处理方法
CN112410588A (zh) * 2020-11-18 2021-02-26 东北大学 一种氟碳铈矿的焙烧工艺

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US8597600B2 (en) 2007-05-21 2013-12-03 Orbite Aluminae Inc. Processes for extracting aluminum from aluminous ores
US8337789B2 (en) 2007-05-21 2012-12-25 Orsite Aluminae Inc. Processes for extracting aluminum from aluminous ores
US9260767B2 (en) 2011-03-18 2016-02-16 Orbite Technologies Inc. Processes for recovering rare earth elements from aluminum-bearing materials
US9410227B2 (en) 2011-05-04 2016-08-09 Orbite Technologies Inc. Processes for recovering rare earth elements from various ores
US9382600B2 (en) 2011-09-16 2016-07-05 Orbite Technologies Inc. Processes for preparing alumina and various other products
US10174402B2 (en) 2011-09-16 2019-01-08 Orbite Technologies Inc. Processes for preparing alumina and various other products
US9023301B2 (en) 2012-01-10 2015-05-05 Orbite Aluminae Inc. Processes for treating red mud
US9556500B2 (en) 2012-01-10 2017-01-31 Orbite Technologies Inc. Processes for treating red mud
CN102605198B (zh) * 2012-01-13 2013-09-25 东北大学 一种氟碳铈矿的分解方法
CN102605198A (zh) * 2012-01-13 2012-07-25 东北大学 一种氟碳铈矿的分解方法
US9181603B2 (en) 2012-03-29 2015-11-10 Orbite Technologies Inc. Processes for treating fly ashes
US9290828B2 (en) 2012-07-12 2016-03-22 Orbite Technologies Inc. Processes for preparing titanium oxide and various other products
US9353425B2 (en) 2012-09-26 2016-05-31 Orbite Technologies Inc. Processes for preparing alumina and magnesium chloride by HCl leaching of various materials
US9534274B2 (en) 2012-11-14 2017-01-03 Orbite Technologies Inc. Methods for purifying aluminium ions

Also Published As

Publication number Publication date
CN1093115A (zh) 1994-10-05
AU4024693A (en) 1994-10-24
EP0692035A1 (fr) 1996-01-17
JP3415844B2 (ja) 2003-06-09
NO953786D0 (no) 1995-09-25
NO953786L (no) 1995-09-25
JPH08508543A (ja) 1996-09-10
DE69318315D1 (de) 1998-06-04
WO1994023075A1 (fr) 1994-10-13
AU682307B2 (en) 1997-10-02
NO307660B1 (no) 2000-05-08
CN1042145C (zh) 1999-02-17
RU2114204C1 (ru) 1998-06-27

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